全文获取类型
收费全文 | 433篇 |
免费 | 26篇 |
国内免费 | 1篇 |
专业分类
化学 | 328篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 52篇 |
物理学 | 75篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 6篇 |
2021年 | 11篇 |
2020年 | 7篇 |
2019年 | 16篇 |
2018年 | 13篇 |
2017年 | 7篇 |
2016年 | 23篇 |
2015年 | 16篇 |
2014年 | 10篇 |
2013年 | 23篇 |
2012年 | 22篇 |
2011年 | 40篇 |
2010年 | 16篇 |
2009年 | 12篇 |
2008年 | 28篇 |
2007年 | 27篇 |
2006年 | 25篇 |
2005年 | 33篇 |
2004年 | 22篇 |
2003年 | 22篇 |
2002年 | 13篇 |
2001年 | 7篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 5篇 |
1994年 | 6篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1989年 | 3篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1968年 | 1篇 |
1966年 | 1篇 |
1939年 | 1篇 |
排序方式: 共有460条查询结果,搜索用时 15 毫秒
31.
Fredin NJ Zhang J Lynn DM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(13):5803-5811
Atomic force microscopy (AFM) and scanning electron microscopy (SEM) coupled with ellipsometry have been used to characterize the microscale and nanoscale structures of erodible multilayered films fabricated from degradable polyamine 1 and either sodium poly(styrene sulfonate) (SPS) or plasmid DNA. Striking differences were found in the topography, structures, and erosion profiles of these two materials upon incubation in PBS buffer at 37 degrees C. For films fabricated from SPS, AFM data are consistent with an erosion process that occurs uniformly without the generation of holes or pits over large, micrometer-scale areas. By contrast, films fabricated from plasmid DNA undergo structural rearrangements to present surface-bound particles ranging in size from 50 to 400 nm. Additional characterization of these particulate structures by SEM suggested that they are interpenetrated with or fused to underlying polyelectrolyte layers on the silicon surface, providing a potential mechanism to manipulate the adhesive forces with which these particles are bound to the surface. The erosion profile observed for polymer 1/SPS films suggests that it may be possible to design assemblies that release two film components with well-defined release kinetics. In the context of gene delivery, the presentation of condensed DNA as nanoparticles at these surfaces may be advantageous with respect to stimulating the internalization and processing of DNA by cells. A quantitative understanding of the factors influencing the fabrication, structure, and erosion profiles of these materials will be useful for the design of multilayered assemblies for specific applications in which controlled film erosion or the release of therapeutic materials is desired. 相似文献
32.
This research extends the study of temporal resolution of the tactual sensory system through measurements of temporal-onset order discrimination for continuous tonal signals addressing (a) the effects of frequency separation of the two stimuli whose onset orders are to be discriminated and (b) the effects of redundant coding of frequency and site of stimulation on performance. Sinusoidal signals were presented either at two separate digits (thumb and index finger of the left hand) or at a single site of stimulation (left index finger) using a multifinger tactual stimulation system. Measurements were obtained using a one-interval two-alternative forced choice procedure in which each interval consisted of the random-order presentation of two different stimuli with roving values of amplitude and duration. Thresholds were estimated from psychometric functions of d' as a function of stimulus-onset asynchrony (SOA). On average, temporal onset-order thresholds were larger for one-finger conditions (mean SOA of 74.8 ms) than for two-finger conditions (mean SOA of 48.5 ms) and decreased as frequency separation increased, particularly for single-site presentation. Redundant coding of frequency and site of stimulation resulted in higher resolution by a factor of 1.5 compared to frequency alone and by a factor of 1.2 compared to site alone. 相似文献
33.
The bicyclic core of octosyl acid A has been prepared using a diastereoselective acetylide addition and 6-endo selenoetherification as key steps. A detailed study of the selenoetherification reaction and difficulties encountered in the conversion of a phenyl group to a carboxylic acid will be discussed. 相似文献
34.
Tactual temporal-onset order thresholds were measured for two sinusoidal vibrations of different frequencies delivered to two separate locations (thumb and index finger) of a multi-finger tactual stimulating device. The frequency delivered to the thumb was fixed at 50 Hz and that to the index finger at 250 Hz. The amplitude and duration of each of the two sinusoidal vibrations were roved independently from trial to trial in a 1-interval, 2AFC procedure. Performance, measured as a function of stimulus-onset asynchrony (SOA), indicated that the temporal-onset-order threshold averaged 34 ms across four subjects. The data were further classified into subsets according to both the amplitude and duration of the two stimuli in each trial of the roving-discrimination paradigm. The results indicated that the amplitude differences of the two stimuli in each trial had a substantial effect on onset-order discrimination, while duration differences generally had little effect. The effects of amplitude differences are explained qualitatively in terms of amplitude latency relationships and stimulus interactions such as temporal masking. Overall, the results not only contribute to an enhanced understanding of the temporal sensitivity of the tactual system but also provide guidelines for the design of tactual aids for hearing-impaired persons. 相似文献
35.
36.
Nathaniel Cain Alexander Haywood George Roberts Douglas Kiserow Ruben Carbonell 《Journal of Polymer Science.Polymer Physics》2011,49(15):1093-1100
The influence of dissolved propane (up to 31.2 wt %) on the phase equilibria of 5 wt % polystyrene (PS) dissolved in 66/34 wt % trans/cis‐decahydronaphthalene (DHN) was measured over the temperature range of 323–423 K. A suitable temperature, pressure, and propane composition operating space was defined to measure intrinsic viscosities of a single fluid phase. Intrinsic viscosities of PS in cosolvent mixtures of propane and trans/cis‐DHN were measured between 323 and 423 K and between 70 and 208 bar. The addition of propane to the isomeric mixture of DHN resulted in a decreased solvent quality for PS, causing a contraction of the PS coil. The most dramatic decrease in solvent quality with the addition of propane occurred at 323 K and 70 bar with approximately a 36% reduction in the viscometric radius with the addition of 45 mol % propane to DHN. At 423 K, the solvent quality was less sensitive to the addition of propane and only a 13% reduction in the viscometric radius was observed at 70 bar and 45 mol % propane in DHN. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 相似文献
37.
The nature of water's interaction with biomolecules such as proteins has been difficult to examine in detail at atomic resolution. Solution NMR spectroscopy is potentially a powerful method for characterizing both the structural and temporal aspects of protein hydration but has been plagued by artifacts. Encapsulation of the protein of interest within the aqueous core of a reverse micelle particle results in a general slowing of water dynamics, significant reduction in hydrogen exchange chemistry and elimination of contributions from bulk water thereby enabling the use of nuclear Overhauser effects to quantify interactions between the protein surface and hydration water. Here we extend this approach to allow use of dipolar interactions between hydration water and hydrogens bonded to protein carbon atoms. By manipulating the molecular reorientation time of the reverse micelle particle through use of low viscosity liquid propane, the T(1ρ) relaxation time constants of (1)H bonded to (13)C were sufficiently lengthened to allow high quality rotating frame nuclear Overhauser effects to be obtained. These data supplement previous results obtained from dipolar interactions between the protein and hydrogens bonded to nitrogen and in aggregate cover the majority of the molecular surface of the protein. A wide range of hydration dynamics is observed. Clustering of hydration dynamics on the molecular surface is also seen. Regions of long-lived hydration water correspond with regions of the protein that participate in molecular recognition of binding partners suggesting that the contribution of the solvent entropy to the entropy of binding has been maximized through evolution. 相似文献
38.
The addition of carbon and heteroatom nucleophiles to (bicyclo[5.1.0]octadienyl)Fe(CO)(2)L(+) cations 5 or 8 (L = CO, PPh(3)) generally proceeds via attack at the dienyl terminus on the face of the ligand opposite to iron to generate 6-substituted (bicyclo[5.1.0]octa-2,4-diene)iron complexes (11 or 13). In certain cases, these products are unstable with respect to elimination of a proton and the nucleophilic substituent to afford (cyclooctatetraene)Fe(CO)(2)L (4 or 7). Decomplexation of 13f, arising from addition of phthalimide to 8, gave N-(bicyclo[5.1.0]octa-3,5-dien-2-yl)phthalimide (19). Oxidative cleavage of 19 (RuCl(3)/NaIO(4)) followed by esterification gave the cyclopropane diester 22, which upon hydrolysis gave cis-2-(2'-carboxycyclopropyl)glycine (CCG-III, 18) (eight steps from 4, 43% overall yield). This methodology was also utilized for preparation of stereospecifically deuterated CCG-III (d-18) and optically enriched (-)-18. Deprotonation of 22 resulted in cyclopropane ring opening to afford the benzoindolizidine (23). 相似文献
39.
Chitin synthase polymerizes UDP-GlcNAc to form chitin (poly-beta(1,4)-GlcNAc) and is essential for fungal cell wall biosynthesis. The alternating orientation of the GlcNAc residues within the chitin chain has led to the proposal that chitin synthase possesses two active sites. We report the results of the first direct test of this possibility. Two simple uridine-derived dimeric inhibitors are shown to exhibit 10-fold greater inhibition than a monomeric control, consistent with the presence of two active sites. This observation has important implications for the development of antifungal agents, as well as the understanding of polymerizing glycosyltransferases. 相似文献
40.
Leibfarth FA Schneider Y Lynd NA Schultz A Moon B Kramer EJ Bazan GC Hawker CJ 《Journal of the American Chemical Society》2010,132(42):14706-14709
The functionalization and cross-linking of polyethylene is synthetically challenging, commonly relying on highly optimized radical based postpolymerization strategies. To address these difficulties, a norbornene monomer containing Meldrum's acid is shown to be effectively copolymerized with polyethylene using a nickel α-iminocarbaxamidato complex, providing high-melting, semicrystalline polymers with a tunable incorporation of the functional comonomer. Upon heating the copolymer to common polyethylene processing temperatures, the thermolysis of Meldrum's acid to ketene provides the desired reactive group. This simple and versatile methodology does not require small molecule radical sources or catalysts, and the dimerization of the in situ generated ketenes is shown to provide tunable cross-linking densities in polyethylene. Subsequent rheological and tensile experiments illustrate the ability to tune cross-linked polyethylene properties by comonomer incorporation and elucidate valuable structure/property relationships in these materials. This study illustrates the power of well-defined and synthetically accessible functional groups in polyolefin synthesis and functionalization. 相似文献